Photographic element and process

ABSTRACT

Photographic elements having a support on which is coated a layer including a light-sensitive halocarbon and a 1,4-pyran derivative like 1-(p-N,N-dimethylaminophenyl)-1H-3-(pethoxyphenyl)naphtho(2,1-b)pyran or 4-(p-N,Ndimethylaminophenyl)-2-phenyl-4H-1-benzo(b)pyran yield printout images in exposed areas on exposure to actinic rays. The resultant printout image can be intensified by heating.

United States Patent Van Allan et al.

[451 Feb. 15, 1972 [54] PHOTOGRAPHIC ELEMENT AND PROCESS [72] Inventors:James A. Van Allan; Dennis E. De Meyer, both of Rochester, N.Y.; FrankD. Allen,

, deceased, late of Rochester, NY.

[73] Assignee: Eastman Kodak Company, Rochester,

[22] Filed: Mar. 2, 1970 211 Appl. No.: 15,867

[52] US. Cl ..96/48 R, 96/90, 96/90 PC [51] Int. Cl. 5/24, G036 1/72 I58] Field of Search ..96/90, 90 PC, 48

I56] References Cited UNITED STATES PATENTS 3,486,899 l2/l969 Brown..96/90 3,121,633 2/1964 Sprague et a]. ..96/90 3,532,638 10/1970 Otis..96/90 PC X Primary Examiner-Norman G. Torchin AssistantExaminerRichard E. Fichter AttorneyW. H. J. Kline, J. R. Frederick andD. M. De Leo [57] ABSTRACT The resultant printout image can beintensified by heating.

9 Claims, No Drawings PHOTOGRAPHIC ELEMENT AND PROCESS This inventionrelates to photography and particularly to photographic elements andprocesses for forming printout images.

It is known that certain halocarbons and polyhalocarbons are lightsensitive and yield photographic products which are capable of producingcolored materials from such colorless materials as certain dyes, anddiarylamines. Examples of this light sensitivity can be found inMechanisms and Structures In Organic Reaction, Gould, page 744; and inU.S. Pat. Nos. 3,102,810 and 3,121,633; in British Pat. Nos. 916,779 and719,919. These references are based on the photoreaction ofpolyhalocarbons with leuco dyes to yield the corresponding colored formsof the dyes.

While polyhalocarbons havingbeen employed separately as light-sensitiveaddenda for certain photographic processes and elements. They have notbeen combined with 4H-pyran derivatives to prepare photographic printoutelements.

Accordingly, an object of this invention is to provide novelphotographic elements. 7

Another object of this invention is to provide new photographic elementsuseful in preparing printout images.

Still another object of the present invention is to provide novelphotographic elements including, as the image-forming components, atleast one halocarbon and at least one 4H- pyran derivative.

An additional object of this invention is to provide a new photographicprocess for producing printout images.

Other objects and advantages of this invention will become increasinglyapparent from a reading of the following specification and appendedclaims.

The objects of this invention are accomplished both with photographicelements wherein a support is coated with a layer including alight-sensitive halocarbon and a 4H-pyran derivative and with aphotographic process for the preparation of printout images including.imagewise exposing an element such as described above to actinic rays.

4H-pyran derivatives useful in the photographic elements of thisinvention include those having at least one aromatic substituent on thepyran ring. Especially desirable are those substituted at the 2-positionand at the 4-position, with at least one of these substituents being anaromatic radical which itself can be still additionally substituted.Additionally the pyran nucleus is desirably fused to an aromatic nucleusto form, for example, a benzopyran or a [2, l -b]naphthopyran.

Particularly advantageous pyran derivatives include those having theformula:

wherein a. each of R and R represent either a hydrogen atom, an alkylradical or an aryl radical and at least one of R or R is an arylradical, b. each of R and R, when taken alone, represents a hydrogenatom, and

c. R and R, when taken together, represent the atoms necessary tocomplete an aromatic ring system.

As defined herein, the term alkyl radical refers to straight andbranched chain alkyl radicals having from one to about four carbon atomslike methyl, ethyl, 2-methoxyethyl, propyl, isopropyl, n-butyl, or thelike, etc. The alkyl radical can be additionally substituted, e.g.,ethoxycarbonylcyanomethyl, ethoxycarbonylbenzoylmethyl, nitromethyl,etc. Alkoxy radical refers to alkoxy radicals having from one to aboutfour carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc., andpreferably methoxy or ethoxy. The term aryl radical designates aromaticsubstituted or unsubstituted aryl radicals having from six to 10 carbonatoms in the nucleus, and including such aryl radicals as phenyl,naphthyl, p-tolyl, p-ethoxyphenyl, p-dimethylaminophenyl and the like.Also as used herein, the designation aromatic ring system refers to amono or poly cyclic, carbocyclic aromatic nucleus like benzene,naphthalene, anthracene, phenanthrene, etc., which is completed by theatoms represented by R and R taken together and is fused to the parentpyran ring between the adjacent carbon atoms substituted by R and R.

Especially advantageous pyran derivatives as described herein includethose wherein R represents either a hydrogen atom, a methyl radical, anN,N-dimethylaminophenyl radical or a p-methylphenylthio radical and Rrepresents a phenyl radical including substituted phenyl radicals likep-ethox yphenyl, N,N-dimethylaminophenyl and the like. Still otherespecially desirable pyran compounds include those wherein R and R whentaken together, represent a 1,4-buta-1,3- dienylene radical (i.e.,CH=CH-CH:CH) with R and R thereby completing a benzene nucleus.

Preferred 4l-l-pyran derivatives useful in the photographic elements ofthis invention include TABLEl Compound l l-(p-N,N-dimethylaminophenyh-lH-3-(pethoxyphenyhnaphthol2,I-h]pyran, 2l-(p-N,N-dimethylaminophcnyl)-lH-3- phenylnaphthol2,l-b]pyran, 34-(p-N,N-dimethylaminophenyl)-2-phenyl-4H-lbenzol blpyran 42-(p-N,N-dimethylaminophenyl)-4H-benzo[blpyran 5lH-3-(p-N,N-dimethylaminophcnyl)naphlhol2,l-hlpyran, 6 2-hcnyl-4H-bcnzo[blpyran. 7l-(p-mlylthio)-1H-3-(p-cthnxyphenyl)naphtho-l2,1-

blpyran. 8 2-ethoxyphenyl-4-(p-tolyllhio)-4H-benzn|blpyran, 9 l(l-ethoxycarbonyl-l-cyanomethyl)-l H-3-(pethoxyphenyUnaphlhol2,l-b]pyran, l0 4-( l-ethoxycarbonyl-l-eyanomethyl)-2-phcnyl-4H-benzolhlpyran, lll(l-cthoxycarbonyl-1-benzoylmcthyl)1H-3-(pethoxyphenyUnaplhoIZ. l-blpyran. and 12 l-nitromethyl-lH-3-(p-N.N-

dimethylaminophcnyl)naphthol-hlpyran.

Also included in the present photographic elements, in

combination with at least one pyran derivative like those mentionedhereinabove is at least one halocarbon or polyhalocarbon compound. Thepyran derivatives and halocarbon compounds are generally combined hereinin weight ratios of from about 3:1 to about 1:5 respectively, andpreferably in substantially equal amounts by weight. Useful halocarboncompounds include, for example, a-halocarbonyl compounds like 01,01,04-tribromoaceto-phenone, poly(vinyl halides) such as poly(vinyl bromide)as well as perhalides and the like. Especially desirable halocarboncompounds are those known to be decomposed by exposure to actinic rays(i.e., ultraviolet and blue light) and which are not acidic. Preferredhalocarbon compounds of this type include polyhalocarbons having threehalogen atoms chemically bonded to a terminal carbon atom, ie, thosehaving the formula R -C-(X) wherein X represents a halogen atom and Rrepresents either a halogen atom, an alkyl radical, a haloalkyl radical,an aryl radical or an aroyl radical. Exemplary polyhalogens include suchcompounds as polyhaloalkanes like iodoform, carbon tetrabromide,pentabromoethane, hexabromoethane, hexachloroethane andtribromophenylmethane. Bromo and iodo compounds are especially preferredclue to their inherently greater light sensitivity as compared to thatof the corresponding chloro compounds. Polyhalocarbons, such asiodoform,

which can be inactivated or diffused from a coated layer on heattreatment are also preferred since they permit convenient stabilizationof the photographic image by the application of heat.

In addition to pyran derivatives and halocarbon compounds, thephotographic elements of this invention can contain additional addenda,e.g., sensitizers or addenda to enhance storage stability or eitherimage quality or raw stock or image stability. As an example, certainnitrogen containing compounds promote the photographic speed andresultant image density at any given exposure level. These materials arewell known in the photographic art and include such compounds as5dimethylaminocoumarin, 6-diethylamino-4- methylcoumarin, carbazole,diphenylformamide, 4- dimethylaminobenzaldehyde, phenothiazine and thelike.

As well as sensitizing addenda, materials which inhibit prematurereaction in the sensitive layers are useful inclusions. Presumably, suchcompounds, which can be included singly or in combination and admixture,function to buffer the imageforming components against a pH change,i.e., to an acidic pH, which would promote a premature printoutreaction. Desirable stabilizing materials include nitrogen-containingheterocycles like benzimidazole, Z-methylbenzimidazole, 2-styrylbenzimidazole as well as related nitrogen containing compoundssuch as azoles like isoazole, triazole, benzotriazole, etc., azinecompounds like pyrimidine, pyrazine, benzopyrimidine and other diazinesor triazine compounds such as l,2,4-triazine, 1,2,3-triazine,l,3,5-triazine, etc.

Other useful addenda materials include image stabilizers, they beingcompounds which enhance the resistance of a resultant photographic imageagainst deterioration from subsequent exposure to heat, light or thelike energies which can cause fading or discoloration of the image.Exemplary such stabilizers include thiazine compounds like phenothiazineand oxines such as alkoxyboroxines.

Generally, the image-forming components and additional stabilizing orother modifying addenda are dispersed in a hydrophobic film-formingresin binder to promote the formation of a coated layer. Desirableresinous matrix vehicles include those which have a softening pointsufficiently high to resist tackiness at the temperature ranges, i.e.,up to about l50 C., useful for intensifying or stabilizing photographicimages produced on elements of this invention. Additionally, the pH ofthe resin binder should not be such that it either promotes or undulyinhibits, i.e., more than do the described stabilizers, theimage-forming reaction. Exemplary matrix vehicles, having the notedcharacteristics, can be selected from a wide variety of materials,including natural resins, modified natural resins and synthetic resins.Exemplary useful natural resins are balsam resins, colophony andshellac. Exemplary suitable modified natural resins arecolophony-modified phenol resins and other resins listed below with alarge proportion of colophony. Suitable synthetic resins include theextensive variety ofsynthetic resins, for example, polymers, such asvinyl polymers including a polyvinyl chloride, polyvinylidene chloride,polyvinyl acetate, polyvinyl acetals, polyvinyl ether and polyacrylicand polymethacrylic esters; polystyrene and substituted polystyrenes orpolycondensates, e.g., polyesters, such as phthalate resin, terephthalicand isophthalic polyesters, maleinate resin and colophony-mixed estersof higher alcohols; phenol-formaldehyde resins, includingcolophony-modified phenol-formaldehyde condensates, aldehyde resins,ketone resins, polyamides and polyadducts, e.g., polyurethanes.Moreover, high-melting polyolefins, such as various polyethylenes,polypropylenes, polyisobutylenes and chlorinated rubber are suitable.Additional useful resinous binder materials are known to those skilledin the polymer arts.

To prepare a composite photographic element of this invention, theimage-forming components and such supplemental addenda compounds as aredesired are generally dissolved or dispersed in a solution of matrixvehicle to prepare a coating composition which can then be applied to asupport material by solvent coating techniques. In a coatingformulation, the halocarbon and pyran derivative are generally presentin stoichiometric amounts or with an excess of pyran derivative.Modifying addenda, if included, can be present in widely varying amountsand the chosen amount will depend on both the selection and quantitiesof image-forming components as well as the modifying effect desired.Conventionally they are included in an amount of from about 1 to about35 percent by weight of the image-forming ingredients. The image-formingcompositions, including stabilizers or other modifying addenda aregenerally incorporated into a coating formulation in an amount of fromabout 5 to about 50 parts by weight per parts by weight of matrixvehicle. Advantageously, the composite coating formulation contains fromabout 5 to about 20 weight percent solid for ease of coating, althoughwider variations can be used if desired for particular situations.

Coating can be accomplished by a wide variety of techniques includingflow coating, doctor blade coating, whirl coating, extrusion hoppercoating, etc. The support material onto which the light-sensitive layeris applied is widely variable and includes such supports as cellulosicmaterials like cellulose acetate, cellulose acetate butyrate, etc., aswell as polystyrenes, polycarbonates, polyvinyl compounds likepolyvinylacetals, polyesters such as poly(ethylene terephthalate),poly-a-olefins like polyethylene, polypropylene and other poly-a-olefinsconventionally having from two to 10 carbon atoms, and including metalslike zinc and aluminum and paper including polyethylene andpolypropylene coated papers.

Subsequent to coating and drying to form a composite photographicelement of this invention, the resultant element can be imagewiseexposed to actinic rays to prepare visible printout images. Afterexposure, heating like that previously described can be employed tointensity or stabilize the lightinduced photographic image.Stabilization, as noted above, is accomplished by exhausting unreactedhalocarbon from the layer. lntensification results from the heatpromoted action of an image intensifier like those described herein.Desirably, heating is within a range of from about 100 to about C., butwider variations in temperature can be used if desired.

The following examples are included for a further understanding of theinvention.

EXAMPLE 1 A solution of 0.15 g. ofcompound l,from Table I, 0.15 g. of6-diethylamino-4-methylcoumarin, 0.3 g. of carbon tetrabromide, and 0.03g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to llml. of a 10 percent solution of poly(vinyl butyral) dichloroethane andmethanol (51]). The resulting solution is doctor blade coated on a papersupport at a wet thickness of0.004 inch and allowed to dry. Theresultant element is then exposed through a negative transparency in anOzamatic Printer, manufactured by the Ozalid Corp., at a lineartransport speed of 8 ft./min. to obtain a dark green, positive image ona white background. The Ozamatic printer uses a 1,200 watt high-pressuremercury arc lamp as an exposure source. Heat treatment for 10 seconds at150 C. increases the image density, and stabilizes the print againstfurther light reaction.

EXAMPLE 2 A solution of0.l5 g. of compound 3, from Table l, 0.15 g. of6-diethylamino-4-methylcoumarin, 0.35 g. of carbon tetrabromide, and0.03 g. of 2-methylbenzimidazole in 4 ml. of dichloroethane is added to11 ml. of a poly(vinyl butyral) solution as in Example 1. The resultingsolution is doctor blade coated on a paper support at a wet thickness of0.004 inch and allowed to dry. The resultant element is then exposed andheated as in Example 1 to obtain an intensified, stable dark blue imageon a light blue background.

EXAMPLE 3 To 4 ml. of a percent solution of a styrene-butylmethacrylatecopolymer in dichloroethane is added a solution of 25 mg. of compound 1from Table l, 25 mg. of carbon tetrabromide, 2.5 mg. of2-methyl-benzimidazole, and 10 mg. of 6-diethylamino-4-methylcoumarin in1 ml. dichloroethane. This solution is doctor blade coated on a papersupport at a wet thickness of 0.004 inch and allowed to dry. Theresultant element is exposed as in Example 1, but at a linear speed of 5ft./min. Heat treatment at 150 C. for 10 seconds gives an intensifieddark green, positive image on a white background.

EXAMPLE 4 A solution of 25 mg. of compound 7 from Table l, 5 mg. ofZ-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. of6-diethylamino-4-methyl-coumarin in 1 ml. dichloroethane is added to 4ml. of a 10 percent solution of a styrene-butyl-methacrylate copolymerin dichloroethane. The solution is doctor blade coated on a papersupport at a wet thickness of 0.004 inch and allowed to dry. Theresultant element is exposed and heated as in Example 3 to give anorangebrown image on a light tan background.

EXAMPLE 5 A coating composition as in Example 4 but employing 25 mg. ofcompound 9 from Table l as the color-forming agent is doctor bladecoated on a paper support at a wet thickness of 0.004 inch and allowedto dry. The resultant element is then exposed and heated as in Example 3to give a dark tan, positive image on a pale yellow background.

EXAMPLE 6 A coating composition identical to that in Example 4, exceptemploying 25 mg. of compound 3 from Table l as the color-forming agent,in lieu of compound 7, is coated at a wet thickness of 0.004 inch on apaper support and allowed to dry. The resultant element is then exposedand heated as in Example 3, to provide an intensified blue image on awhite background.

EXAMPLE 7 A coating composition as in Example 3, except employing 25 mg.of compound 10 from Table I as the color-forming agent is doctor bladecoated on a paper support at a wet thickness of 0.004 inch and allowedto dry. When exposed and heated as in Example 3, the resultant elementgives an intensified, stable greenish-yellow image on a whitebackground.

EXAMPLE 8 A solution of 25 mg. of compound 1 1 from Table l, 5 mg. of2-methylbenzimidazole, 25 mg. of carbon tetrabromide, and 10 mg. ofphenothiazine in 1 ml. dichloroethane is added to 4 ml. ofa l0 percentsolution of poly(vinyl butyral) in a mixture of dichloroethane andmethanol (5:1). This solution is doctor blade coated at a wet thicknessof 0.004 inch on a paper support and allowed to dry. The resultantelement is exposed and heated as in Example 3 to provide an intensified,stable yellow-orange image on a light yellow background.

The invention has been described in detail with particular reference topreferred embodiments thereof, but, it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

We claim:

1. A photographic element for the production of printout images andcomprising a support having coated thereon a layer comprising alight-sensitive halocarbon compound that is decomposed on exposure toactinic rays and a 4H-pyran derivative that is a benzopyran or anaphthopyran having at least one aryl group substituted on the pyranring, said pyran and said halocarbon compound being combined in a weightratio of from 3:1 to |:5 respectivel 2. A photographic element as(described in claim I wherein the halocarbon compound is selected fromthe group consisting of halocarbon and polyhalocarbon compounds andwherein the 4H-pyran derivative has the formula:

wherein a. each of R and R represent a member selected from the groupconsisting of a hydrogen atom, an alkyl radical and an aryl radical andat least one of R and R is an aryl radical,

b. each of R and R when taken alone, represents a hydrogen atom, and

c. R and R when taken together, represent the atoms necessary tocomplete an aromatic ring system.

3. A photographic element as described in claim 2 wherein R represents aradical selected from the group consisting of a hydrogen atom, a methylradical, an N,N-dimethylaminophenyl radical, and a p-methylphenylthioradical and R represents a phenyl radical.

4. A photographic element as described in claim 2 wherein R and R whentaken together, represent a l,4-but-l,3- dienylene radical.

5. A photographic element as described in claim 3 wherein the methylradical represented by R is selected from the group consisting of al-ethoxycarbonyl-l-cyanomethyl radical, alethoxycarbonyl-l-benzoylmethyl radical and a nitromethyl radical andthe phenyl radical represented by R is selected from the groupconsisting of a phenyl radical, a p-ethoxyphenyl radical and ap-dimethylaminophenyl radical.

6. A photographic element for the production of printout images andcomprising a support having coated thereon a layer comprising ahalocarbon selected from the group consisting of carbon tetrabromide anddichloroethane and a 4H- pyran derivative as described in claim 3.

7. A photographic element for the production of printout images andcomprising a support having coated thereon a layer comprising a carbontetrabromide and a 4H-pyran derivative selected from the groupconsisting a. l-(p-N,N-dimethylaminophenyl) l H-3-(p-ethoxyphenb.4-(p-N,N-dimethlaminophenyl)2-phenyl-4H- l -benzo[b] pyran c.lH-3-(p-N,N-dimethylaminophenyl)naphtho[2,l-b]- pyran d.l-(p-tolylthio)-lH-3-(p-ethoxyphenyl)naphtho-[2,l-b]

pyran e. 1-( l-ethoxycarbonyl-lcyanomethyl)- lH-3-(p-ethoxyphenyl)naphtho[2,l-b]pyran f. 4-( l-ethoxycarbonyll-cyanomethyl)-2-phenyl-4H- benzo[b]pyran g. l-(l-ethoxycarbonyl-l-ben2oylmethyl)-lH-3-(p-ethoxyphenyl)naphtho[2,l-b]pyranh. l-nitromethyl-lH-3-(p-(N,N-dimethylamino)phenyl)- naphtho[ 2, l -blpyran, said pyran and said carbon tetrabromide being combined in aweight ratio of from 3:1 to 1:5 respectively.

8. A photographic image-forming process for the preparation of printoutimages on a photographic element as described in claim 1, which processcomprises imagewise exposing said element to actinic rays, whereupon aprintout image is produced in exposed ares.

9. A photographic image-forming process as described in claim 8 andadditionally including heating said exposed element to intensify theprintout image.

2. A photographic element as described in claim 1 wherein the halocarboncompound is selected from the group consisting of halocarbon andpolyhalocarbon compounds and wherein the 4H-pyran derivative has theformula:
 3. A photographic element as described in claim 2 wherein Rrepresents a radical selected from the group consisting of a hydrogenatom, a methyl radical, an N,N-dimethylaminophenyl radical, and ap-methylphenylthio radical and R1 represents a phenyl radical.
 4. Aphotographic element as described in claim 2 wherein R2 and R3, whentaken together, represent a 1,4-but-1,3-dienylene radical.
 5. Aphotographic element as described in claim 3 wherein the methyl radicalrepresented by R is selected from the group consisting of a1-ethoxycarbonyl-1-cyanomethyl radical, a1-ethoxycarbonyl-1-benzoylmethyl radical and a nitromethyl radical andthe phenyl radical represented by R1 is selected from the groupconsisting of a phenyl radical, a p-ethoxyphenyl radical and ap-dimethylaminophenyl radical.
 6. A photographic element for theproduction of printout images and comprising a support having coatedthereon a layer comprising a halocarbon selected from the groupconsisting of carbon tetrabromide and dichloroethane and a 4H-pyranderivative as described in claim
 3. 7. A photographic element for theproduction of printout images and comprising a support having coatedthereon a layer comprising a carbon tetrabromide and a 4H-pyranderivative selected from the group consisting a.1-(p-N,N-dimethylaminophenyl)1H-3-(p-ethoxyphenyl)naptho (2, 1-b)pyranb. 4-(p-N,N-dimethlaminophenyl)-2-phenyl-4H-1-benzo(b)pyran c.1H-3-(p-N,N-dimethylaminophenyl)naphtho(2,1-b)-pyran d.1-(p-tolylthio)-1H-3-(p-ethoxyphenyl)naphtho-(2,1-b)pyran e.1-(1-ethoxycarbonyl-1-cyanomethyl)-1H-3-(p-ethoxyphenyl)naphtho(2,1-b)pyranf. 4-(1-ethoxycarbonyl-1-cyanomethyl)-2-phenyl-4H-benzo(b)pyran g.1-(1-ethoxycarbonyl-1-bEnzoylmethyl)-1H-3-(p-ethoxyphenyl)naphtho(2,1-b)pyran h.1-nitromethyl-1H-3-(p-(N,N-dimethylamino)phenyl)-naphtho(2,1-b)pyran,said pyran and said carbon tetrabromide being combined in a weight ratioof from 3:1 to 1:5 respectively.
 8. A photographic image-forming processfor the preparation of printout images on a photographic element asdescribed in claim 1, which process comprises imagewise exposing saidelement to actinic rays, whereupon a printout image is produced inexposed ares.
 9. A photographic image-forming process as described inclaim 8 and additionally including heating said exposed element tointensify the printout image.